Formaldehyde → HCID 86690385, compound

HRID 513894Notes

Reaction equation

HRID 513894 reaction equation
[C:1]([O:4][C@@H:5]([C@:16]12[CH2:51][C:50](=[O:52])[C:49]([CH:53]([CH3:55])[CH3:54])=[C:17]1[C@@H:18]1[C@@:31]([CH3:34])([CH2:32][CH2:33]2)[C@@:30]2([CH3:35])[C@@H:21]([C@:22]3([CH3:48])[C@@H:27]([CH2:28][CH2:29]2)[C:26]([CH3:37])([CH3:36])[C@@H:25]([O:38][C:39](=[O:47])[CH2:40][C:41]([CH3:46])([CH3:45])[C:42]([OH:44])=[O:43])[CH2:24][CH2:23]3)[CH2:20][CH2:19]1)[CH2:6][NH:7][CH2:8][C:9]1[CH:14]=[CH:13][C:12]([Cl:15])=[CH:11][CH:10]=1)(=[O:3])[CH3:2].C=O.[BH3-][C:59]#N.[Na+]>CO>[C:1]([O:4][C@@H:5]([C@:16]12[CH2:51][C:50](=[O:52])[C:49]([CH:53]([CH3:55])[CH3:54])=[C:17]1[C@@H:18]1[C@@:31]([CH3:34])([CH2:32][CH2:33]2)[C@@:30]2([CH3:35])[C@@H:21]([C@:22]3([CH3:48])[C@@H:27]([CH2:28][CH2:29]2)[C:26]([CH3:37])([CH3:36])[C@@H:25]([O:38][C:39](=[O:47])[CH2:40][C:41]([CH3:45])([CH3:46])[C:42]([OH:44])=[O:43])[CH2:24][CH2:23]3)[CH2:20][CH2:19]1)[CH2:6][N:7]([CH2:8][C:9]1[CH:10]=[CH:11][C:12]([Cl:15])=[CH:13][CH:14]=1)[CH3:59])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 5003444Sodium cyanoborohydrideHCID 86690382HCID 86690382, compound

Product 1

HCID 86690385HCID 86690385, compoundYield 78.7%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 4-(((3aR,5aR,5bR,7aR,9S,11aR,11bR,13aS)-3a-((S)-1-acetoxy-2-((4-chlorobenzyl)amino)ethyl)-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-3,3a,4,5,5a,5b,6,7,7a,8,9,10,11,11a,11b,12,13,13a-octadecahydro-2H-cyclopenta[a]chrysen-9-yl)oxy)-2,2-dimethyl-4-oxobutanoic acid (50) (150 mg, 0.192 mmol) in MeOH (6 mL) stirred in air at rt was added formaldehyde (31.2 mg, 0.384 mmol). The reaction mixture was stirred at rt for 2 h. Then it was added NaCNBH3 (85 mg, 1.345 mmol) portionwise and stirred for overnight. The solvent was evaporated and the residue diluted with DCM and washed with water and brine. The dried organics were filtered and concentrated to give 4-(((3aR,5aR,5bR,7aR,9S,11aR,11bR,13aS)-3a-((S)-1-acetoxy-2-((4-chlorobenzyl)(methyl)amino)ethyl)-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-3,3a,4,5,5a,5b,6,7,7a,8,9,10,11,11a,11b,12,13,13a-octadecahydro-2H-cyclopenta[a]chrysen-9-yl)oxy)-2,2-dimethyl-4-oxobutanoic acid (68) (120 mg, 65% yield) as a white solid. This material was used without further purification. 1H NMR (400 MHz, CHLOROFORM-d) δ=7.31-7.26 (m, 2H), 7.24-7.16 (m, 2H), 5.65 (d, J=8.5 Hz, 1H), 4.50 (br. s., 1H), 3.66-3.51 (m, 1H), 3.49-3.36 (m, 1H), 3.27-3.06 (m, 2H), 2.73-2.32 (m, 5H), 2.26 (s, 3H), 2.08-0.73 (m, 49H); LC/MS: m/z calculated 793.5. found 794.3 (M+1)+.

Workup

  1. stirringstirred for overnight
  2. customThe solvent was evaporated
  3. additionthe residue diluted with DCM
  4. washwashed with water and brine
  5. filtrationThe dried organics were filtered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-1ffb928f64f044b0bda403b733b2029e
Source dataset
uspto-grants-2015_08
Patent number
US09102685B2

Reaction notes

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